Monoazo and disazo triazine dyes



1 2945mm MoNoAzo AND DISAZO TRIAZINE DYES Alfred Fasciati, B'ottmingen,Raymond Gunst, Binningen,

Henri 'Riat, Arlesheim, and Karl Seitz, Neu'-Allschwil, Switzerland,assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing.Filed Sept. 9, 1957, Ser. No. 682,583 Claims priority, applicationSwitzerland Sept. 14, 1956 '8 Claims. (Cl. 260- 153) 7 The presentinvention provides new, valuable azoldyestuffs containing at least twostrongly acid, Water-solubiliz- 'ing groups and in addition a2-halogen-4-amino-lz3z5- jtriazine radical attached to the radical of an'azo com- I ponent of the benzene series by way of an amino bridge,preferably a bridge of the formula I in which 12 indicates a positivewhole number. The invention is concerned especially with suchmonoand-disazo dyestuffs as contain a ,2 chloro-4amino-l23:5-triazineradical of which the amino group is a NH group orthe radical of an amine containing at most 12 carbon atoms, whichpreferably contains anacifd watersolubilizing group, i.e. a carboxyl orsulfonic acid group if it comprises an aromatic six-member'ed ring.

Among these dyestuffs primarily the metal-free dyestufrs are of valuewhich correspond to the formula l D-'--N=N-'-iA-NH-X in which Xindicates a 2,-halogen-4-amino-l:3:5 triazine radical, preferably a2-chloro-4amino-1:3z5-triazine radical attached in 6-position to the NH-group, of which the amino group contains at most 12 carbon atomslandwhen it is an aryl' amino group, also contains a sulfonic acid group, Dis the radical of a diazo component, if desired containing azo groupsand A is a benzene'radical attached to the -NH-X+ group in .p-positionto the azo group and in which D and X together contain at least twostrongly acid water-solubilizing groups. I

The characteristic monohalogen-triazi ne grouping is attached to theradical of'the azo component by way of an amino bridge which is attachedto the benzene radical A either directly or by way of a bridge member,for example an alkylene radical.' The radical D can be an unsubstitutedphenyl radical or a methyl, alkoxy, chloro or nitrophenyl radical or astill larger radical, for exam- 7 ple a naphthalene radical or abicyclic radical, if desired containing azo groups.

Together with a monohalogen-triazine substituent of the specified type,the dyestufis ofthe invention also contain at least two strongly acidwater-solubilizing groups such as carboxyl or more especially sulfonicacid groups. Advantageously the dyestuifs contain more than one suchgroup per azo group, i.e. at least two such groups are present in amonoazo dyestufi and at least three in a .2-aminonaphthalene-4 8-, ..-57- or -6 8-disulfonic acid,

2,945,022 Patented July 12, 1 960 2 1 disazo dyestuif. Thesewater-solubilizing groups can be distributed in any manner in thedyestufi molecule.

For the manufacture of the dyestufis of this invention it is possible toproceed from corresponding dyestuffs, prepared by methods of known type,containing a dihalogem, especially a dichloro-1:3:5-triazine radical,and in such dichloro-triazine dyestuffs to replace one of the twochlorine atoms, for example by reaction with ammonia or with an aminecontaining at most 12 carbon atoms and also containing a carboxyl orsulfonic 'acid group if it comprises an aromatic nucleus, by acorresponding radical, i.e. by an amino group. The dihalogen-triazinedyestufis to be used in this case can'be obtained by methods of knowntype by reaction of azo dyestufis containing an acylatable amino groupin the radical of an azo component of the benzene series, with cyanurichalides, especially with cyanuric chloride (2:4:6-trichloro-1z3z5-triazine) in the molecular proportion of at least 1:1 orfrom the corresponding dyestufi" components containing dichlorotriazineradicals. v

For the production of the starting dyestuffs which con train theacylatable amino group in an azo component of the benzene series, thereare concerned, for example, amino benzenes which are capable of couplingowing to the presence of an amino group which is at most secamino groupafter the dyestutt production the w-methane sulfonic acid ishydrolytically split ofi), also m-toluidine and3-acylamino-l-amino-benzenes,- e.g. 3-a cetylamino -'1 aminobenzene,S-hydroxyacetylamino-l-aminobenzene, 3-

carbethoxyamino 1 aminobenzol, 1 amino 2 methyI-S-methoxy-benzene,l-amir'ro-ZzS-dimethoxy- -or diethoxy-benzene, 1-amino-3-methoxybenzeneand l-amino- Z-methoxy-S:isopropyl-benzene. V

The diazo components to be coupled with these azo components can containnonwater-solubilizing substituents,'if desired. also azo groups and mustcon tain strongly acid water-solubilizing"substituents such as sulfonicacid groups. These diazo components can also either be relatively simplecompounds, for example aminobenzene sulfonic acids, amino naphthalenesulfonic acids, amino pyreneor -chrysene sulfonic acids, amino naphtholsulfonic acids or amino phenol sulfonic acids, or complicateddiazotizable compounds containing, for example, one or two azo groups.

As examples of amines of which the diazo compounds3-amino-2-hydroxybenzoic acid-S-sulfonic acid,

3 ramino-6-hydroxy-benzoic acid-S-sulfonic' acid, I

2-aminophenol-4-sulfonic acid, 5-acetylamino-2-aminobenzene-l-sulfonicacid, 4-acetylamino-2-aminobenzene-l-sulfonic acid,

S-acetylaminoor S-benzoylamino-Z-aminobenzene-l-carboxylic acid,

.2-aminobenzoic acid-4- or -5-sulfom'c acid, --'1-aminonaphthalene-4-,-5-, -6- or -7-sulfonic acid, 2-aminonaphthalene-4-, -6-, -7- or-8-sulfonic acid; --"laminonaphthalene-3:6-disulfonic acid,

l-aminobenzene-Z:S-disulfonic acid, i 1

1-(3'- or 4'-aminobenzoyl)-aminobenzene-3-sulfonic acid, 3-aminopyrene8- or -10-monosu1fonic acid, 3-aminopyrene-5z8- or :10-disulfonic acid,4-nitro-4 aminostilbene-2:2'-disulfonic acid, and alsoO-acyl-derivatives of aminonaphthol-sulfonic acids, for

example the O-acyl derivatives of 1-amino-8-hydroxynaphthalene-3:6--or-4;6-disulfonic acid, dehydrothiotoluidine-mono or -disulfonic acid andso on.

mono azo dyestuifs containing sulfonic acid groups that y can beproduced, for example, by coupling of diazotized mono acyl derivativesof aromatic diamines with azo components containing an aromatic hydroxylgroup or a keto methylene group and subsequent hydrolysis of theresulting acylamino monoazo dyestuffs, for example the amino monoazodyestuffs obtainable by hydrolysis of the monoacyl diamino-stilbenedisulfonic acids and the like from phenols, naphthols, 5-pyrazolones,barbituric acids, hydroxyquinolines, ,B-keto carboxylic acid derivativesand diazotized monoacyl diamino benzenes.

There are also suitable as diazotizable aminoazo dyestutfs couplingprod- H ucts from one of the mentioned coupling components containing NHgroups with the diazo compounds of the likewise mentioned amino sulfonicacids. 7

, In this case preferably such starting materials are combined as leadto amino azo dyestutfs with at least two water-solubilizing groups.

The coupling of the diazo compounds, obtained for examplebymeans ofmineral acid, especially hydrochloric .acid, and sodium nitrite, withthe mentioned amines of the benzene series, likewise takesplace bymethods of known type. 7

Prior to the condensation of the resulting aminoazo dyestuffs withcyanuric chloride, the dyestuffs can if deamino compounds withdihalogen-triazine dyestutfs is advantageously carried out with the useof acid-binding agents such as sodium acetate, sodium carbonate orsodium hydroxide, and under such conditions that in the product producedone replaceable halogen atom remains, i.e., for example, inorganicsolvents or at relatively low temperatures in aqueous agents.

The azo dyestuffs of this invention can likewise be prepared by means ofa modification of the process described immediately above. Thismodification of the process consists in that the azo dyestuffsapplicable as starting materialsfor the manufacture of thedichlorotriazine dyestuifs, which contain an acylatable amino group, forexample the aminoazo dyestuffs obtainable from the components set forthabove, are condensed with 2:4-dichloro-6-amino-l:3:5 triazines in such amanner that in the resulting condensation product together with at leasttwo water-solubilizing groups a replaceable halogen atom is alsopresent. r

Suitable 2:4-dihalogen-1:3:5-triazines can be prepared bymethods ofknown type from cyanuric halides such as cyanuric bromide or cyanuricchloride, for example byreacting 1 mol of cyanuricchloride with 1 mol ofammonia or with 1 mol of the amines set forth above. The resultingdihalogen-triazine compounds can for the production of the azo dyestuffsof this invention be condensed with already produced aminoazo dyestuffsof the specified type containing an acylatable amino group.

In the production of the dyestuffs of the invention by condensation ofone of the'specified aminoazo dyestuffs with cyanuric chloride and oneof the likewise specified simpler amino compounds, in most cases thesequence of the condensations can be selected as desired. In spite ofthe presence of labile halogen atoms in the dyestuffs of this inventionthey can, without loss of their. valuable properties, be isolated andworked up to useful, dry dye preparations. The isolation in the processof the invention'preferably takes place at as low a temperature aspossible by salting out and filtration. The filtered dyestuffs can bedried, if desired after the addition of color stretching agents and/orof buffer substances such as mixtures of equal parts of monoand disodium sired, for the introduction of anamino -benzoyl group,

to-be condensed with 3- or 4-nitro benzoyl;chloride. and

after nitrobenzoylation the nitro group converted into an amino group byreduction. r

a The condensation of the resulting aminoazo dyestufis with cyanuricchloride is to be carried out in such a j manner that in the resultingcondensation product two replaceable halogen atoms remain of which oneis replaced according to the present invention by the radical of anamino compound of the specified type. As such amino compounds are hereconcerned ammonia and.

amines such as methyl, dimethyl, ethyl, diethyl, propyl,

isopropyl, butyl, isobutyl, hexyl or cyclohexyl-amine and alsoS-chlorethylamine, piperidine, morpholine, y-methoxy-propylamine,methoxy-ethylamine, eth-anolanrines,

pr'opanolarnines and acylated amines such as acetamide; 3

buty-ric acid amide, urea, thiouzrea, hydrazine, thiosemicarbazide andtoluene sulfonic acid amide, also glycocoll,

sulfonic acid. Only the latter amines containing watersolubilizinggroups are concerned when as starting materials dyestutfs are used whichcontain only one watersolubilizing group. t I 1 'Thecondensation,according ,tothe invention, of these nated with aqueous dyestuifsolutions, if desired also containing salt, and the dyestuffs fixed,preferably in the hot, after an alkali treatment. This process and thedirect dye method which is also applicable in the case of -manyfofthedyestuffs obtained by the present process,

give'valuable dyeings, fixed fast to washing, while by .the printingprocess fast prints are obtained.

. When the dyestutfs contain metal-complex forming groups, for exampleo:o'-di-hydroxy azo groupings or ohydroxyca'rboxy groupings, as forexample in the case of salicylic acid radicals, the dyeings obtainedtherewith can betreated with agents providing metal, for example agentsproviding chromium but preferably agents providing nickel and copper;The treatment with the agents providing metal can be carried out bymethods of known "type.

If desired, very valuable dyeings can be obtainedbyoperatingin;accordancewith the process in which the dye ings" producedwiththe metal-free dyestuffs are aftertreated with aqueoussolutionscontaining water-soluble compounds, especially complex copper compounds,and basic formaldehyde condensation products from comaasaoaa :15 poundscontaining at least once in the molecule the atom or compounds, torexample cyanamide, that can easily be converted into such compounds.

The dyeings obtainable with the new dyestuif preparations upon thecellulosic fibers, and also corresponding prints, are distinguished as arule by the purity of their color shade, by a good tastness to light andprimarily by outstanding fastness to wet processing, especially a verygood fastness to washing. 1

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated and the relationbetween part by weightand part by volume being the same as that betweenthe kilogram and the liter.

EXAMPLE 1 45.1 parts of the amino-disazo dyestufi obtained by couplingdiazotized 2-aminonaphthalene-4:8-disulfonic acid with1-amino-2-methoxy-5 methylbenzene, are dis- H solved in 1500 parts ofwater and sulficient sodium hydroxide to form a neutral solution.This'is treated with an ice-cold aqueous suspension of 18.5 parts ofcyanuric chloride. Then about 100 parts of N-sodium hydroxide solutionare gradually added dropwise so that the reaction mixture reacts weaklyacid or neutral. When free amino washing.

group can no longer be detected, a solution is added,

neutralized with sodium carbonate, from 17.3 .parts ofl-aminobenzene-Ia-sulfonie acid, a further 10 parts of sodiumbicarbonate are added and the whole is stirred for several hours at30-40 C until the condensation is' complete. The dyestufi is salted out,filtered oil and dried. It dyes cotton from a bath containing much salt,

in the presence of'alkali', in reddish yellow shades fast to light andwashing.

The sequence of the condensations can also be reversed, i.e. by firstreacting the 1-aminobenzene-3-sulfonic acid with the cyanuric chlorideand condensing the resulting primary condensation product with the monoazo dyestulf.

EXAMPLE 2 30.3 parts of 2-aminonaphthalene-4:8-disulfonic acid tion areintroduced dropwise in such a manner that the reaction mixturecontinuously exhibits a weakly acid reaction (pH 5.5-6). When free aminogroup can no longer be detected, 35 parts of 10% ammonia solution areintroduced and stirring carried out for several hours at 3040 C. Thedyestuif is then salted out, filtered off and dried under vacuum. Theresulting yellow powder dissolves in water with a yellow color and dyescotton from a bath containing much salt, in the presence of alkali, inreddish yellow shades very fast to light and The following table showsthe results of condensation by the methods of Examples 1 and 2ofcyanuric chloride on the one hand with the aminoazo dyestuifs obtainedby coupling from the dyestuflf components mentioned in columns I and IIand on the other hand with the amines mentioned in column 'I-II. Similarmonochlorotriazin'e dyestuifs are obtained, which dye cotton by theso-called pad dyeing process in the shades set out in column IV.

Table l I II III IV Dlazo component Coupling component Amine 1 2Amlnonaphthalene 1-Am1no-2-methoxy-fireddish yellow.

. szs-dlsulfonlc acid. methyl-benzene. 2 r n z Do, "2 r n r 0 D0, 4 r nr 0 D0, 5 r n r 0 Do, 6 0 r0 Do, 7 0 do Dlmethylamlne Do. 8 o doCyclohexylamlne Do. 9 n (in Mo phnlino D0, 10 do do1-Aminobenzone-2-sul- Do.

' tonic acid. 11 do 2-Ammonaphthalene-6- Do.

* sulfonlc acid. 12 do l-Amino-Zzfi-dl-methoxy-1-Aminobenzene-2-sulorange. benzene. tonic acid. 13 -.do1-Amino-3-methyl-bon- H3 reddish yellow.

. zone. 14 do 1 -Amlno -2 -methoxy- NH; yellow.

' benzene. 15 l-Amlnonaphthalene- 1 Amino 2 methoxy NH; yellowishorange.

3:6-disulfonic acid. 5-methylbenzene. 16 2-Amlnonaphthalenedo NH reddishyellow. 5:7-di sultonle acid. 17 z-Amlnonaphthalene- 1 Amino 3 acetylMethylamine Do.

4:8-dlsulfonlc acid. aminobenzene. 18 do do Ethylnmino Do, to do rlnIsobutylamine Do. 20 do do Tam-inn D0, 21 do do 1 Amlnobenzene 3 D0.

, sulfonamide. 22 do d o 1 Aminonaphthalene-t Do.

sulfonic acid. .23 do -Butylam.ine Do. 24 do do Mornhnlino D0, 25 do2-Amlnoethanol Do. 26. do -Methoxypropylamine Do. 27 do2-Amino-1-propanol- Do. 23 do do 1-Am1no-2-propanol D0. 29 do doBenzylamine Do. 30 do .l-Ethylhexylamine Do. U 31 do3-Aminophenylurea..-- NH; Do. 32 do do 1 Amlnobenzene 3 D0.

. sultonlc acid. m I

a i 1 Tamal -Continued 17.3 parts of 1-aminobenzene-2-sulfonie acid aredissolved in 300 parts of water with the addition of 5.3

parts of sodium carbonate. The resulting neutral solu tion is allowed toflow with good stirring into an ice- M cold suspension of 18.5 parts ofcyanuricchloride and' NaQaS I 80 :Na

in 2000 parts of water. Stirring is carried out for 55v V I I I1 III IVDlazocomponent Coupling component Amine 33 1 Aminonaphthalene 1 Amino 3acetyl NH reddish yellow.

azfi-disulfonic acid. aminobenzene.

34 2 Aminonaphthalene -.-do NH Do.

:7- disulfonic acid.

35 1 Aminobenzene -2:5 NH- yellow.

. disnltonic acid.

36 1 Aminobenzene 4 .do NH Do.

carboxylic acid-3-sulfonic acid.

37 2 (4 Aminophenyl) do NR3. yellow orange.

benzthiazole X,3' r disulfonic acid. a

38 .do do 1 Aminobenzene 3 Do.

7 .sulfonic acid. 39 2 Aminonaphthalene 1 Amino 3 methane N H; reddishyellow.

4:8-disultonic acid. sulfonyl amino benzone.

1 Amino e3 propion NH; Do.

ylaminobenzene. 1 Amino 3 -.methyl z-Arninoethanol D'o. benzene. g rinIsopropylamine Do. 1 Methylamino 3 NH; Do.

methylbenzene. n 1 -.Aminobenzene 2 Do.

. sulfonic acid. 1 Amino 2 methyl NH; Do.

5 acetylaminobcn Do. 7 zene. g n r l Amino 2 methoxy N'Ha'. yellowishorange.

' 5 acetyl amino -benr zene. V Y

47 O Benzene -sulfonyl 1-Amino-2-rnet hoxy- NH reddish orange.

ester of 1-amino-8-hy-. fi-methyl benzene.

droxynaphthalene- 3:6-disulfonic acid.

1 Aminobenzene 2 do 1' Aminobenzene 2 reddish yellow.- sulfonic acid. 7sulfonic acid. I r n 2 Aminonaphthalene do 4-An1ino-1:1-"diphenyl: Do.

4:8-disulfonie acid. 4-sulfonio acid; n U .do Thiosemicarbazide Do; .dodo Phenylhydrazine m Do. sulfonic acid. I 52 do Amino-acetic acid 7 Do.

and drying, it forms adark orange'powder and dyes cot- EXAMPLE 3 tonfirom an alkaline bath contaimng much salt in yellow orange shades veryfast to light and washing.

5 1.8 parts of the aminodisazo dyestulf obtained by cou- 'pling theacetic acid solution of diazotized 4-amino-l:lazobenzene-3:4'-disulfonicacid with l-amino-3-acetylaminobenzene are dissolved in 3,000 parts ofwater with the addition of 10.6 parts of anhydrous sodium carbonate.

The solution is added to an ice-cold aqueous suspension of 18.4 parts ofcyanuric chloride and the mixture well stirred. Then about 100 parts ofsodium hydroxide solution are slowly added dropwise, whereby the pH ofthe reaction mixture is maintained between 6.5 and 7.5.

When free amino group can no longer be detected, 35 parts of ammoniasolution are added and stirring carried out for 6 hours at -40 C. Thedyestufi is eral hours at C. with gradual neutralization oftlie. mineralacid formedby addition of 10% sodium car bonate solution. When aminogroup can no longerbe.

detected, the solution is brought to pH 8.5 with sodium carbonate andthedyestufi salted out. After filtration salted out, filtered and dried. Itdissolves in water with an-orange color and dyes cotton from an alkalinebath containing much salt in yellow orange shades very fast to light andwashing.

By Busing for the condensation with cyanuric chloride the compounds ofcolumn III of Table II below on the one hand and on theo'ther hand theaminoazo dyestuff obtained by coupling one of the azo components ofcolumn II with the 'diaizo compounds of the aminoazo dyestuffs mentionedincolumn I, dyestuffs are obtained which dye cotton in the shades setout in column IV.

Table II I n m 1v 1 4-Amino-1:1'-azobenzene-3:4-disul1onicacid1-Amino-3-methylbenzena.-- NH: yellow brown. 2 do I dol-Acrirgnobenzened-slfltonie Do.

- 4 a r 8 do- 1-Amino-2:5-dimethylben- NH: Do.

zene. 4 .-do- 'lrAln inobenzene-snllonic Do.

ac B dn 1-Amino-2-methoxy-5-me NH; .L brown orange.

thylbenzene. I I v 1 q 6 ..do do l-Aliztllinobenzened-slflfonle Do..-

ac 7 .do... l-Amino-ii-acetylaminol-Aminobenzene-B-srflfonio yelloworange. I

. benzene. acid. V B do ..'.do l-Aminobenzene-Z-sultonic- Do.

0 I 1-Amino-3-methylbenzene... io.-.' Do.

I NH:

SOIH

H018 CH:

10 N,= do l-Aminot aenzenei-slflfonic Do. P acid.

Ems on,

:1 1-Amino-3-aeeiyl-aminm1-Aminobenzene-2-eu1fonic orange.

benzene. acid.

12 1-Am1no-2-methoxy-5-1 ne- NH; brown orange."

, thylbenzene.

HOlS

OCH:

l-gclilgnenenzene-sulronic Do.

1-A mlno-3-methylbanzene. 1-: ng'nobenzene-2-su1tonic reddish orange.

Anjlir -xi N l h brown orange.

l-Ami no-a-methylnenzenen 1-Amlnobenzena-3-sulfonic rubyrad. I

NH- A red.

Table: II-Continued 1 11 r11 iv l-Arnlno-s-methylbenzene.il-Anainobenzene-S-sultonic red. 8C1

do ..do orange.

SO'IH EXAMPLE 5 What is claimed is: 7 1. An 20 d estufl of the formula 2parts of the dyestufl? of the formula 3 y x m l R--N=N(Ri--N= )ni 1 HO 5OCH: ii a N -NH-o LC -Y N=N C NHC.\ o-Nm .e (L "N I N l Mos-1m t rwherein R is a merhbersele'cted -from the' group consisting of theradicals v I I HOrS SOQH are dissolved in 100 parts of water. -A cottonfabric is impregnated with this solution at 60-80 C. on the foulardandthe excess liquid'is'squeezed err so thatthe"ri1atr=.i'rial- 5retains 75% of its weight of dyestuif solution.

The goods thus impregnated are dried and then im- 1 50811 pregnated atroom temperature with a solution containing and per liter 10 parts ofsodium hydroxide and 300 parts of sodium chloride, squeezed off to aliquid retention of l 75% and steamed for 60 seconds at 100-101 C. Thegoods are then rin's'e'd, treated in an-0.5%-sodium bicarbonatesolution, rinsed, soaped for a quarter of an hour :11 in an 0.3%solution of a non-ionicfwashing agent at boiling temperature, rinsed anddried. A reddish yellow 50 R1 15 member selectedflmm the groupconslstmgof dyeing, fast to washing and light, is obtained. the radlcals EXAMPLE6 Q 2 parts'of' the dyest'ulf of the formula "soin v I om i HOsiJHN-CO-CHo (Ill 7 SOEH 0 and H0 s N=N N=N t O O 00H:

' NH-C "(l-NH; e0

( JHa are dissolved=in 100 parts of water by boiling. The resultingstock solution is added to 2900 parts of water at 20 C. After theaddition of 30 parts of trisodium phosphate and 60 parts of sodiumchloride, 100 parts of n and m each represents a whole positive numberof at most 2; X is a member selected from the group consisting of themethylgroup, the acetylamino group, the

" 'propionylamino group, the 'm'ethanesulfonylaminogroup and the HN-CO--NH group; :and Y represents a member selected from the groupconsisting'of the NH group, the methylamino group, ethylamino group,nbutylam'mo group, hexylalmino" group, isobutylamino group, diethylaminogroup, hydroxyethylamino group, hy-. 'droxybutylamino group, morpholinogroup, 'y-rnethoxypropylamino group, beilzylarnino,group,hydroxypropylamino group, 's'ulfophenylamino" group, sulfonaphthyh,

2,945,022 13 amino group, carboxymethylamino group and the m-sulfophenyl--NH-NH group.

2. The monoazo dyestufis according to claim 1, wherein '14 6. Themonoazo dyestufif which in its free acid state corresponds to theformula 1 S0311 NHOOOH: (131 n 15 3. A monoazo dyestufi which in itsfree acid state 5 corresponds to the formula fi SOaH '-NH-C\%CNHCH2OH2OH cm 01 N SOaH N=N- 10 7. The monoazo dyestufi which in itsfree acid state fi f corresponds to the formula NH-C O-NHB NHCOCH: 01363E I \K I 0 n-l C n1 Zn1 H 0 3S- 4. The monoazo dyestuff which in itsfree acid state H A} corresponds to the formula NH O\ soul CH3 11 N oN=N N N H I SOsH NH-C (J-NH, o l 8. The disazo dyestufi which m its freeacid state corre- S0311 $0118 sponds to the formula UN=N-OSOaH NHCOGH:Z1 H018 Ova-NH SOzH 5. The monoazo dyestufl which in its free acid statecorresponds to the formula 35 isg glig gs gzigig so H CH 01 U1 u I2,653,149 Riat Sept. 22, 1953 2,679,499 Long et a1. May 25, 1954 fi2,820,785 Zollinger et a1. Ian. 21, 1958 NH-C yO-NHa

1. AN AZO DYESTUFF OF THE FORMULA